Selective dehydrohalogenation of tertiary halogenated hydrocarbons and removal of tertiary halogenated hydrocarbon impurities from a halogenated hydrocarbon product

ABSTRACT

A process for converting a tertiary halogenated hydrocarbons in a tertiary halogenated hydrocarbon-containing stream to a corresponding unhalogenated or less-halogenated unsaturated hydrocarbon product with the release of hydrogen halide involves contacting the tertiary halogenated hydrocarbon with a sorbent-type dehydrohalogenation catalyst in a reaction zone and optionally passing a stripping gas through the reaction zone to remove vapor phase reaction products from the reaction zone. A process for removing a tertiary chlorinated hydrocarbon impurity from 1,3-dichloro-1-propene involves contacting a mixture containing the 1,3-dichloro-1-propene and the tertiary chlorinated hydrocarbon impurity with a dehydrochlorination catalyst effective to catalyze a conversion of the tertiary chlorinated hydrocarbon impurity to a corresponding unchlorinated or less-chlorinated unsaturated hydrocarbon and hydrogen chloride and distilling the 1,3-dichloro-1-propene to produce a purified cis-1,3-dichloro-1-propene fraction and a purified trans-1,3-dichloro-1-propene fraction.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims the benefit of U.S. Provisional PatentApplication No. 61/269,594 filed 26 Jun. 2009, which is incorporatedherein by reference in its entirety.

BACKGROUND

The present invention relates to the field of halogenated hydrocarbonsand the manufacture and purification of same, and more particularly, butnot exclusively, relates to processes for dehydrohalogenating tertiaryhalogenated hydrocarbons, which processes have utility, for example, inthe removal of a tertiary halogenated hydrocarbon impurity from amanufacturing process stream.

1,3-Dichloro-1-propene is a useful commercial compound in the medicaland agricultural fields. Dow AgroSciences, Inc., (Zionsville, Ind.)produces a mix of cis and trans isomers of 1,3-dichloro-1-propene underthe trademark Telone II® for use as a soil fumigant to controlnematodes.

1,3-Dichloro-1-propene is a by-product, or co-product, of the chemicalreactions employed to produce allyl chloride, and thus commercial1,3-dichloro-1-propene products can be made by isolating a byproductfraction from an allyl chloride production plant that includes1,3-dichloro-1-propene (referred to herein as a “Telone crude”fraction), and then subjecting the Telone crude to a distillationprocess to separate and recover 1,3-dichloro-1-propene from the otherby-products and impurities that are produced in the allyl chloridemanufacturing process and that separate into the Telone crude fraction.While distillation processing is suitable to achieve desired puritylevels with respect to many of the by-products and impurities in theTelone crude, one particular tertiary chlorinated alkane species,2-chloro-2-methylpentane, cannot effectively be separated from1,3-dichloro-1-propene by distillation to meet desired purity levels.

There exists a need for processes effective to remove a2-chloro-2-methylpentane impurity from 1,3-dichloro-1-propene and, moregenerally, a need to remove tertiary halogenated hydrocarbon impuritiesfrom a hydrocarbon product. The present application addresses theseneeds and provides additional benefits.

SUMMARY

In one aspect, the present application provides methods, systems anddevices for dehydrohalogenating one or more tertiary halogenatedhydrocarbons.

In another aspect of the present application, there are providedmethods, systems and devices for removing one or more tertiaryhalogenated hydrocarbon impurity, such as, for example, a tertiarychlorinated alkane or alkene impurity, from a mixture of halogenatedhydrocarbon compounds. In one embodiment, the tertiary halogenatedhydrocarbon is removed from a manufacturing process stream or a wastestream. The method includes selectively dehydrohalogenating the one ormore tertiary halogenated hydrocarbons and removing reaction products ina stripping gas and/or by distillation. Such methods, and correspondingsystems and devices, are useful, for example, in industrial processesfor purifying one or more halogenated target compounds. In oneembodiment, there is provided a method for removing a2-chloro-2-methylpentane impurity from 1,3-dichloro-1-propene.

Further embodiments, forms, features, advantages, aspects, and benefitsshall become apparent from the following description and drawings.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with one embodiment of the present application.

FIG. 2 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 3 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 4 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 5 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 6 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 7 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 8 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 9 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 10 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

FIG. 11 is a schematic view of a 1,3-dichloro-1-propene purificationsystem in accordance with another embodiment of the present application.

DETAILED DESCRIPTION

For the purpose of promoting an understanding of the principles of theinvention, reference will now be made to the embodiments illustrated inthe drawings and specific language will be used to describe the same. Itwill nevertheless be understood that no limitation of the scope of theinvention is thereby intended. Any alterations and further modificationsin the described embodiments, and any further applications of theprinciples of the invention as described herein are contemplated aswould normally occur to one skilled in the art to which the inventionrelates.

In one aspect, the present application relates to the discovery ofcertain techniques for selectively dehydrohalogenating tertiaryhalogenated hydrocarbons to convert the tertiary halogenated hydrocarboninto a corresponding lesser-halogenated or non-halogenated alkeneaccompanied by the release of hydrogen halide (i.e., hydrogen chloride,hydrogen fluoride and/or hydrogen bromide). As used herein, the term“tertiary halogenated hydrocarbon” refers to a hydrocarbon in which acarbon bound to three carbon neighbors (i.e., a tertiary carbon) is alsobound to a halogen, and which includes a beta hydrogen. In oneembodiment, the tertiary halogenated hydrocarbon is a tertiarychlorinated alkane or alkene. In another embodiment, the tertiaryhalogenated hydrocarbon is a tertiary halogenated alkane, such as, forexample, a tertiary chlorinated alkane. In yet another embodiment, thetertiary halogenated hydrocarbon comprises 2-chloro-2-methylpentane.Because the dehydrohalogenation catalysts described herein are effectiveto selectively dehydrohalogenate tertiary halogenated hydrocarbons in amixture without altering other halogenated hydrocarbons in the mixture,catalyzed dehydrohalogenation reactions described herein can be employedin processes for purifying halogenated hydrocarbon products. Thus,another aspect of the application relates to the dehydrohalogenation ofone or more tertiary halogenated hydrocarbons as an additional treatmentphase of an industrial distillation process for enhancing the puritylevels of one or more target compounds.

In certain aspects of the present application, attention is given to thedehydrochlorination of tertiary chlorinated hydrocarbons and the removalof tertiary chlorinated hydrocarbons from a flow stream mixture thatincludes one or more tertiary chlorinated hydrocarbon and otherhalogenated hydrocarbons. It is to be understood, however, that thepresent application also contemplates application of the principlesdescribed herein to tertiary halogenated hydrocarbons that comprisehalogens other than chlorine. In addition, while one or more embodimentsdescribed herein involve the dehydrochlorination of tertiary chlorinatedalkanes, the present application also contemplates application of theprinciples described herein to tertiary halogenated alkenes, such as,for example, 4-chloro-4-methyl-1-pentene, or other tertiary halogenatedhydrocarbons that include a beta hydrogen. Therefore, for purposes ofthe present specification, embodiments relating to tertiary chlorinatedalkanes are also intended to apply to tertiary halogenated hydrocarbons,whether alkanes, alkenes, or other hydrocarbons having a halogen bondedto a tertiary carbon and comprising a beta hydrogen, as if each of thesealternative embodiments were expressly named.

In a process for converting tertiary halogenated hydrocarbons tocorresponding less-halogenated or non-halogenated alkenes and hydrogenhalide according to the present application, the tertiary halogenatedhydrocarbons are contacted with a sorbent-type dehydrohalogenationcatalyst. It has been discovered that commercially effective conversionrates can be achieved by effecting the catalyzed reaction in the liquidphase at a temperature less than the dew point of the mixture containingthe tertiary halogenated hydrocarbon reactant or in the vapor phase at atemperature above the dew point of the mixture. In one embodiment, thecatalyzed reaction is effected at a temperature of less than about 135°C. Conducting the reaction in the liquid phase can be effective in someembodiments to save the energy that would otherwise be necessary tovaporize the process stream; however, in other embodiments, such as, forexample, where a process stream is already in the vapor phase, thereaction can be performed in the vapor phase without input ofsignificant amounts of energy.

The dehydrohalogenation catalyst utilized in the methods and systemsdescribed herein is a sorbent-type dehydrohalogenation catalyst. As usedherein, the terms “dehydrohalogenation catalyst,” “dehydrochlorinationcatalyst,” “sorbent-type dehydroahlogenation catalyst,” “sorbent-typedehydrochlorination catalyst” and “sorbent-type catalyst” are usedinterchangeably to refer to a traditional adsorbent that includessilicon oxide and/or aluminum oxide, such as, for example, activatedalumina (aluminum oxides), sintered alumina (aluminum oxide), activatedclay (silicon and aluminum oxides), fumed silica or silica gel (siliconoxide), and magnesium silicate (a silicon oxide). In one embodiment, thesorbent-type catalyst is in its natural form, i.e., without having beenpretreated with any special doping or metals. Representativecommercially available activated clay catalysts that can be used in theprocesses described herein include, for example, mordenite, which iscommercially available from a number of zeolite suppliers such asSud-Chemie Inc. (Louisville, Ky.) and Tonsil™, which is commerciallyavailable from Sud-Chemie Inc. (Louisville, Ky.). In one embodiment theactivated alumina catalyst comprises a neutral grade activated aluminaor an acidic grade activated alumina. A representative commerciallyavailable activated alumina catalyst that can be used in the processesdescribed herein is F-200 activated alumina, which is commerciallyavailable from BASF Catalysts LLC (Iselin, N.J.). In another embodiment,the catalyst comprises an acidic or neutral aluminum oxide catalyst thathas been sintered to reduce the surface area and acidity. Materials ofthis type are commercially available from BASF Catalysts LLC (Iselin,N.J.). In other embodiments, the catalyst is a silica gel or a zeolite.

The selective catalyzed dehydrohalogenation reaction can be conducted ina reactor defining a reaction chamber in which the catalyst iscontained. The tertiary halogenated hydrocarbon, or a mixture containingsame, is passed through the reaction chamber in contact with thecatalyst. In one embodiment, an inert stripping gas is also passedthrough the reaction chamber. The stripping inert gas operates to removethe hydrogen halide reaction product from the reaction chamber, therebyhelping to drive the equilibrium of the reaction toward the productside. Depending upon the reaction temperature, the addition of the inertgas also increases the percentage of the feed that is in the vapor phasein the reactor. The stripping gas can comprise any inert gas. As usedherein, the term “inert gas” refers to any compound or element that is astable gas at a temperature and under conditions present in thedehydrohalogenation reactor, such as nitrogen, helium, argon or lighthydrocarbon.

The catalyst can have a variety of physical forms suitable for achievingan acceptable level of contact with the reactant(s), many examples ofwhich are well known to persons skilled in the art. Preferred forms arethose that provide high surface area for contact with the reactant(s).For example, and without limitation, the catalyst can be provided in aparticulate form in a packed bed or a fluidized bed or in a structuredform, such as, for example, structured packing or baffles as describedfurther hereinbelow.

Reaction conditions in which the reactants are in the liquid phase or inthe gas phase when contacted with the catalyst are suitably employed,but a gas phase reaction is presently preferred. In one embodiment inwhich the catalyzed reaction is conducted in the liquid phase,prescribed reaction conditions, as conducted with a packed bed, afluidized bed or a structured form, include maximum catalyst temperatureof about 125° C., a pressure of from about 0.5 to about 50 psia,stripping gas flow rates from 0 to about 4000 hr-1 gas hourly spacevelocity (GHSV) and liquid feed flow rates from 0 to about 4000 weighthourly space velocity (WHSV). In another embodiment, in which thecatalyzed reaction is conducted in the gas phase, prescribed reactionconditions, as conducted with a packed bed, a fluidized bed or astructured form, include maximum catalyst temperature of about 200° C.,a pressure of from about 0.5 to about 100 psia, stripping gas flow ratesfrom 0 to about 4000 hr-1 gas hourly space velocity (GHSV) and gaseousfeed flow rates from 0 to about 4000 hr-1 gas hourly space velocity(GHSV).

In one embodiment, the reaction is carried out at a temperature of fromabout 20 to about 150° C. In another embodiment, the reaction is carriedout at a temperature of from about 50 to about 125° C. In yet anotherembodiment, the reaction is carried out at a temperature of from about60 to about 115° C. In still another embodiment, the reaction is carriedout at a temperature of from about 90 to about 105° C. In still yetanother embodiment, the reaction is carried out at a temperature of fromabout 90 to about 125° C. In yet another embodiment, the reaction iscarried out at a temperature of from about 90 to about 115° C.

In one embodiment, the reaction is carried out at a pressure of fromabout 0.5 to about 50 psia. In another embodiment, the reaction iscarried out at a pressure of from about 5 to about 30 psia. In yetanother embodiment, the reaction is carried out at a pressure of fromabout 10 to about 25 psia. In still another embodiment, the reaction iscarried out at a pressure of from about 14 to about 20 psia. In stillyet another embodiment, the reaction is carried out at atmosphericpressure.

The catalyzed dehydrohalogenation reactions discussed above can beadvantageously employed to remove a tertiary halogenated alkane and/ortertiary chlorinated alkene impurity from a target compound or mixture,such as, for example, from a halogenated hydrocarbon compound or amixture including one or more halogenated hydrocarbon compounds. This iscommercially useful, for example, to purify a target compound or mixturein a manufacturing process stream that includes one or more tertiaryhalogenated alkane and/or tertiary halogenated alkene impurities or torecover hydrogen halide and hydrocarbons from a waste stream thatincludes one or more tertiary halogenated alkanes and/or tertiarychlorinated alkenes. The methods and systems described herein can alsobe employed as a production technique to produce specific hydrocarboncompounds from tertiary halogenated hydrocarbons.

With regard to the removal of a tertiary halogenated alkane and/ortertiary halogenated alkene impurity from a compound or mixture, amethod includes dehydrohalogenating one or more tertiary halogenatedalkane and/or tertiary halogenated alkene using a dehydrohalogenationcatalyst as described above, together with one or more distillationtreatments. One embodiment of the present application is a method forseparating and recovering 1,3-dichloro-1-propene from a flow stream thatalso includes one or more tertiary chlorinated alkane and/or tertiarychlorinated alkene impurities. The method includes contacting the flowstream with a suitable sorbent-type catalyst for conversion of the oneor more tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurity in the flow stream into one or more corresponding alkenes,i.e., corresponding unchlorinated or less-chlorinated unsaturatedhydrocarbons, and hydrogen chloride. The corresponding alkenes producedin the reactor are readily distillable from 1,3-dichloro-1-propene, andthus conversion of the tertiary chlorinated alkane and/or tertiarychlorinated alkene impurities to corresponding unchlorinated orless-chlorinated alkenes, followed by distillation can effectivelyremove the tertiary chlorinated alkane and/or tertiary chlorinatedalkene impurities from 1,3-dichloro-1-propene. In one embodiment, thereaction products, along with any other impurities that may be present,are distilled in a two column configuration, a first column effective toseparate and purify the trans isomer of 1,3-dichloro-1-propene, and thesecond column effective to separate the cis isomer of1,3-dichloro-1-propene from impurities. This process allows for theproduction of a more highly purified 1,3-dichloro-1-propene productcompared to processes known and used in the prior art, and assists inmeeting heightened purity standards.

Referring now to FIG. 1, there is shown one illustrative process schemefor purifying a 1,3-dichloro-1-propene product. Feed stream 15 of system10 includes 1,3-dichloro-1-propene and at least one tertiary chlorinatedalkane and/or tertiary chlorinated alkene impurity. In one embodiment,feed stream 15 comprises a mixed cis- and trans-1,3-dichloro-1-propeneproduct that includes a tertiary chlorinated alkane and/or tertiarychlorinated alkene impurity, such as the commercially available TeloneII® pesticide product, which is a commercially available mixture of cis-and trans-1,3-dichloro-1-propene that includes some residual tertiarychlorinated alkane and/or tertiary chlorinated alkene impurities, suchas, for example, the tertiary chlorinated alkane2-chloro-2-methylepentane, the tertiary chlorinated alkane2-chloro-2,3-dimethylbutane and/or the tertiary chlorinated alkene4-chloro-4-methyl-1-pentene. Alternatively, feed stream 15 can be a1,3-dichloro-1-propene product having similar purity levels to TeloneII®, or even having lower purity levels. In this embodiment, feed stream15 can be derived at least in part from an associated same-site processof making a mixed cis- and trans-1,3-dichloro-1-propene product, such asa commercial process for making Telone II®. System 10 is used toincrease the purity level of the Telone II® product.

In another embodiment, feed stream 15 comprises a byproduct fraction ofan allyl chloride manufacturing plant that includes cis- andtrans-1,3-dichloro-1-propene and various other byproducts of the allylchloride manufacturing plant that separate into the1,3-dichloro-1-propene fraction. For example, feed stream 15 can bederived at least in part from an associated same-site process for makingallyl chloride. An example of such a suitable feed stream is stream 26of the allyl chloride process depicted in FIG. 1 of InternationalApplication Number PCT/US95/14354, published as InternationalPublication Number WO 97/03035, which is incorporated herein byreference in its entirety. Stream 26, or a mixture similarly composed of1,3-dichloro-1-propene and tertiary chlorinated alkanes and/or tertiarychlorinated alkenes, is referred to herein as “Telone crude,” andtypically includes cis- and trans-1,3-dichloro-1-propene and at leastone tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurity, such as, for example, the tertiary chlorinated alkane2-chloro-2-methylepentane, the tertiary chlorinated alkane2-chloro-2,3-dimethylbutane and/or the tertiary chlorinated alkene4-chloro-4-methyl-1-pentene.

In the process depicted in FIG. 1, purified 1,3-dichloro-1-propeneproduct 64 is produced by a multi-step process including a reaction thatconverts tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities to corresponding unchlorinated or less-chlorinated alkenesand hydrogen chloride, and a plurality of distillation separationtreatments. Specifically, feed stream 15 is fed into catalytic reactor20 that defines a reaction chamber (also referred to herein as“dehydrochlorination reaction zone” or “reaction zone”), where it iscontacted with a sorbent-type catalyst to convert tertiary chlorinatedalkanes and/or tertiary chlorinated alkenes in feed stream 15 tocorresponding unchlorinated or less-chlorinated alkenes and hydrogenchloride. Reaction temperatures, pressures and other reaction parameterscan be as described above, provided that the reaction temperature inthis embodiment is preferably from about 20 to about 130° C. and thepressure is preferably from about 5 to about 30 psia. In anotherembodiment, the temperature is from about 80 to about 120° C. In yetanother embodiment, the temperature is from about 100 to about 110° C.In still another embodiment, the pressure is from about 10 to about 25psia. In still yet another embodiment, the pressure is from about 14 toabout 20 psia.

Catalytic reactor 20 is also configured to receive optional strippinggas flow stream 22 and to pass a stripping gas through the reactionchamber. The stripping gas operates to remove the correspondingunchlorinated or less-chlorinated alkene and hydrogen chloride reactionproducts from the reaction chamber of catalytic reactor 20, therebyhelping to drive the equilibrium of the reaction toward the products.After passage through the reaction chamber of reactor 20, the strippinggas can be processed to remove hydrogen chloride and other reactionproducts entrained therein, and can optionally be recycled through thereaction chamber. In other embodiments, stripping gas flow stream 22 isabsent. Reaction zone effluent 24 (also referred to herein as “phase 2reaction mixture 24”) exits reactor 20.

Reaction zone effluent 24 exiting reactor 20 includes a reducedconcentration of tertiary chlorinated alkane and/or tertiary chlorinatedalkene impurities compared to feed stream 15. Reaction zone effluent isthen conveyed to vapor liquid separator and cooler 30 to separatecomponents of reaction zone effluent 24 into first gaseous lightsfraction 32, which can be recovered or disposed of via any conventionalmeans, for example, by incineration, and first liquid fraction 34, whichincludes cis- and trans-1,3-dichloropropene and distillable impurities.

First liquid fraction 34 is then fed into first distillation separator40, also referred to herein as the “trans distillation column” or “transcolumn,” which is effective to separate and purify the higher boilingtrans isomer of 1,3-dichloro-1-propene by removing a low boilingcomponent 44 containing the cis-isomer and impurities from the top ofseparator 40 and recovering purified trans-1,3-dichloro-1-propene 46from separator 40 as a high boiling component. In a case where feedstream 15 includes other low boiling other components, such as, forexample, C₃ compounds or other low boiling other components, these areseparated and recovered together with the cis-isomer in low boilingcomponent 44. Separator 40 is also effective to separate tar fraction48, which can be recovered from the bottom of separator 40 and disposedof via any conventional means, for example, by incineration.

First distillation separator 40 can be a conventional distillationcolumn, also referred to in the industry as a distillation unit or adistillation tower. In the purification scheme depicted in FIG. 1, firstdistillation separator 40 is operated at a distillation temperatureeffective to separate the cis and trans isomers of1,3-dichloro-1-propene from one another. In one embodiment, thedistillation temperature of first distillation separator 40 is atemperature of from about 20 to about 110° C. In another embodiment, thedistillation temperature of first distillation separator 40 is atemperature of from about 50 to about 90° C. The pressure is preferablya medium to deep vacuum. For example, in one embodiment, the pressurefor distillation in separator 40 is a pressure of from about 30 mmHg toabout 760 mmHg. In another embodiment, the pressure is from about 330 toabout 370. In one embodiment, first distillation separator 40 is adistillation tower having from about 20 to about 90 equilibrium stages.In another embodiment, first distillation separator 40 is a distillationtower having from about 60 to about 80 equilibrium stages. In alternateembodiments, first distillation separator 40 can be set up for use in abatch distillation system or a continuous distillation system.

The cis isomer of 1,3-dichloro-1-propene and the low boiling impuritiespresent in first liquid fraction 34 are separated and recovered from thetop of first distillation separator 40. As used in connection withseparator 40 of this embodiment, the term “low boiling” refers tocompounds having boiling points lower than the boiling point of thetrans isomer of 1,3-dichloro-1-propene, which tend to separate with thecis isomer in first distillation separator 40. Residual high boilingcomponent 46 comprises the purified trans-isomer. In the embodimentdepicted in FIG. 1, first distillation separator 40 is also configuredto remove remaining lights from fraction 34 via second gaseous lightsfraction 42 and to remove tars from fraction 34, both of which can bedisposed of via any conventional means.

Low boiling component 44 containing the cis-isomer recovered from firstdistillation separator 40 is then conveyed to second distillationseparator 50, also referred to herein as the “cis distillation column”or “cis column,” which is effective to purify the cis isomer of1,3-dichloro-1-propene present in component 44 by removing mid-boilingimpurities 56 from the bottom of separator 50 and removing third gaseouslights fraction 52 from the top of separator 50, both of which can bedisposed of via any conventional means. As used in connection withseparator 50 of this embodiment, the term “mid-boiling impurities”refers to compounds having boiling points higher than the boiling pointof the cis isomer of 1,3-dichloro-1-propene, which can be separated fromthe cis isomer by accumulating in the bottom of separator 50. Purifiedcis-1,3-dichloro-1-propene is recovered from second distillationseparator 50 in fraction 54.

Second distillation separator 50, like separator 40, can be aconventional distillation column. In one embodiment, the distillationtemperature of second distillation separator 50 is a temperature of fromabout 20 to about 110° C. In another embodiment, the distillationtemperature of second distillation separator 50 is a temperature of fromabout 50 to about 100° C. The pressure is preferably a medium to deepvacuum. For example, in one embodiment, the pressure for distillation inseparator 50 is a pressure of from about 30 to about 760 mmHg. Inanother embodiment, the pressure is from about 520 to about 560 mmHg. Inone embodiment, second distillation separator 50 is a distillationtower. There is no particular limit to the theoretical plate number ofthe distillation tower used as second distillation separator 50.However, in one embodiment, second distillation separator 50 is adistillation tower having from about 20 to about 90 equilibrium stages.In another embodiment, second distillation separator 50 is adistillation tower having from about 55 to about 75 equilibrium stages.In alternate embodiments, second distillation separator 50 can be set upfor use in a batch distillation system or a continuous distillationsystem.

Purified trans-1,3-dichloro-1-propene 46 and purifiedcis-1,3-dichloro-1-propene 54 are then fed to mixer 60, where they aremixed in predetermined proportions to provide product 64, which is amixture of purified cis- and trans-1,3-dichloro-1-propene that possessesknown utility as a soil fumigant and nematocide. For example, product 64can be a more highly purified commercial grade Telone II® product. Inother embodiments, purified trans-1,3-dichloro-1-propene 46 and purifiedcis-1,3-dichloro-1-propene 54 are not mixed, but are instead used, sold,shipped or stored separately. For purposes of the present description,it is to be understood that the term “purified” does not connote that agiven compound or fraction is entirely free from impurities. Rather,this term is intended to refer to a degree of purity higher than areference material, such as, for example, a mixture that is fed into adistillation separator.

Because tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities commonly found in a Telone crude feed stream havedistillation profiles similar to cis-1,3-dichloro-1-propene, they tendto separate with the cis stream when distilled without priordehydrochlorination. Therefore, the present application alsocontemplates placement of a dehydrochlorination reactor at a differentlocation in the process. With reference to the embodiment depicted inFIG. 2, for example, dehydrochlorination reactor 120 is positioned afterfirst distillation separator 140 (i.e., after the trans column). Morespecifically, feed stream 115 is fed into first distillation separator140, which is effective to separate and purify the higher boiling transisomer of 1,3-dichloro-1-propene by removing a low boiling component 144containing the cis isomer and impurities from the top of separator 140and recovering purified trans-1,3-dichloro-1-propene 146 from separator140 as a high boiling component. Tertiary chlorinated alkanes and/ortertiary chlorinated alkenes present in feed stream 115 separate withcis isomer component 144. In a case where feed stream 115 includes otherlow boiling other components, such as, for example, C₃ compounds orother low boiling components, these are also separated and recoveredtogether with the cis-isomer in low boiling component 144 or as firstgaseous lights fraction 142. Separator 140 is also effective to separatetar fraction 148, which can be recovered from the bottom of separator140.

First distillation separator 140, like separator 40 in FIG. 1, can be aconventional distillation column, can have a configuration as describedabove in connection with separator 40, and can be operated at similardistillation temperatures and pressures as described above in connectionwith separator 40. In alternate embodiments, first distillationseparator 140 can be set up for use in a batch distillation system or acontinuous distillation system.

As stated above, the cis isomer of 1,3-dichloro-1-propene and the lowboiling impurities, including tertiary chlorinated alkanes and/ortertiary chlorinated alkenes, are present in low boiling component 144.As used in connection with separator 140 of this embodiment, the term“low boiling” refers to compounds having boiling points lower than theboiling point of the trans isomer of 1,3-dichloro-1-propene, which tendto separate with the cis isomer fraction 144 in first distillationseparator 140. In the high boiling component 146, the purifiedtrans-isomer will be contained. In the embodiment depicted in FIG. 2,first distillation separator 140 is also configured to remove remaininglights from feed stream 115 via first gaseous lights fraction 142 and toremove tars from feed stream 115 in distillation separator 140.

Component 144, which includes the cis isomer of 1,3-dichloro-1-propeneand also impurities, including tertiary chlorinated alkane and/ortertiary chlorinated alkene impurities, is fed into a reaction chamberof catalytic reactor 120, where it is contacted with a sorbent-typecatalyst to convert tertiary chlorinated alkanes and/or tertiarychlorinated alkenes in component 144 to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride. The reaction of tertiarychlorinated alkanes and/or tertiary chlorinated alkenes is carried outat a temperature and pressure, and under conditions similar to thosedescribed above in connection with reactor 20. Catalytic reactor 120 isalso optionally configured to receive stripping gas flow stream 122 andto pass the stripping gas through the reaction chamber, thereby removingreaction products in the vapor phase that are produced in catalyticreactor 120. After passage through the reaction chamber of reactor 120,the stripping gas can then be processed to remove hydrogen chloride andother reaction products entrained therein, and can optionally berecycled through the reaction chamber. In other embodiments, strippinggas flow stream 122 is absent. Reaction zone effluent 124 (also referredto herein as “phase 2 reaction mixture 124”) exits reactor 120.

Reaction zone effluent 124 exiting reactor 120 includes a reduced amountof tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities compared to component 144. Reaction zone effluent is thenconveyed to vapor liquid separator and cooler 130 to separate componentsof reaction zone effluent 124 into first gaseous lights fraction 132 andrough cis fraction 134, which includes cis-1,3-dichloropropene anddistillable impurities.

Rough cis fraction 134 is then fed into second distillation separator150, also referred to herein as the “cis distillation column” or “ciscolumn,” which is effective to purify the cis isomer of1,3-dichloro-1-propene present in fraction 134 by removing mid-boilingimpurities 156 from the bottom of separator 150 and removing thirdgaseous lights fraction 152 from the top of separator 150. As used inconnection with separator 150 of this embodiment, the term “mid-boilingimpurities” refers to compounds having boiling points higher than theboiling point of the cis isomer of 1,3-dichloro-1-propene, which can beseparated from the cis isomer by accumulating in the bottom of separator150. Purified cis-1,3-dichloro-1-propene 154 is recovered from seconddistillation separator 150.

Second distillation separator 150, like separator 50 in FIG. 1, can be aconventional distillation column, can have a configuration as describedabove in connection with separator 50, and can be operated at similardistillation temperatures and pressures as described above in connectionwith separator 50. In alternate embodiments, second distillationseparator 150 can be set up for use in a batch distillation system or acontinuous distillation system.

Purified trans-1,3-dichloro-1-propene 146 and purifiedcis-1,3-dichloro-1-propene 154 are then fed to mixer 160, where they aremixed in predetermined proportions to provide product 164, such as, forexample, a purified Telone II® product. In other embodiments, purifiedtrans-1,3-dichloro-1-propene 146 and purified cis-1,3-dichloro-1-propene154 are not mixed, but are instead used, sold, shipped or storedseparately.

In the systems described above, the tertiary chlorinated alkane reactoris positioned in a process flow stream either before or after a transcolumn. One of the advantages of the dehydrochlorination catalystsdescribe herein is that the conversion of tertiary chlorinated alkanesand/or tertiary chlorinated alkenes to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride can occur in the liquidor gaseous phase. Thus, a variety of embodiments are possible in whichthe reaction is caused to occur within one or more of the distillationcolumns during distillation processing. For example, in the embodimentdepicted in FIG. 3, system 210 includes reactor 220 positioned withinfirst distillation separator 240. In this embodiment, reactor 220 can bea packed bed reactor or can comprise baffles or other structures thatare made of the catalytic material and that are positioned within firstdistillation separator 240.

In operation of the system set forth in FIG. 3, feed stream 215 is fedinto first distillation separator 240 (trans column) having reactor 220positioned therein. Separator 240 is effective to separate and purifythe higher boiling trans isomer of 1,3-dichloro-1-propene while at thesame time converting tertiary chlorinated alkanes and/or tertiarychlorinated alkenes in feed stream 215 to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride. Low boiling component244 containing the cis-isomer and impurities, including the newlygenerated products of the catalyzed dehydrochlorination reaction oftertiary chlorinated alkanes and/or tertiary chlorinated alkenes inreactor 220, are recovered from the top of separator 240 and purifiedtrans-1,3-dichloro-1-propene 246 is recovered from separator 240 as ahigh boiling component. In a case where feed stream 215 includes otherlow boiling other components, such as, for example, C₃ compounds orother low boiling other components, these are separated and recoveredtogether with the cis-isomer in low boiling component 244. Separator 240is also effective to separate first gaseous light fraction 242 from thetop of separator 240 and tar fraction 248, which can be recovered fromthe bottom of separator 240.

In the purification scheme described in connection with FIG. 3, firstdistillation separator 240, like separator 40 in FIG. 1, can be similarto a conventional distillation column, can have a configuration asdescribed above in connection with separator 40, and can be operated atsimilar distillation temperatures and pressures as described above inconnection with separator 40, with the proviso that separator 240 ismodified to include therein reactor 220, which can comprise, forexample, a packed bed of sorbent-type catalyst particles or,alternatively, baffles made of sorbent-type catalyst materials. Inalternate embodiments, first distillation separator 240 can be set upfor use in a batch distillation system or a continuous distillationsystem.

The cis isomer of 1,3-dichloro-1-propene and the low boiling impurities,including alkenes and hydrogen chloride produced by catalyticdehydrochlorination of tertiary chlorinated alkanes and/or tertiarychlorinated alkenes in reactor 220, are present in low boiling component244 separated and recovered from the top of first distillation separator240. As used in connection with separator 240 of this embodiment, theterm “low boiling” refers to compounds having boiling points lower thanthe boiling point of the trans isomer of 1,3-dichloro-1-propene, whichlow boiling compounds tend to separate with the cis isomer fraction 244in first distillation separator 240. In the high boiling component 246,the purified trans-isomer will be contained. In the embodiment depictedin FIG. 3, first distillation separator 240 is also configured to removelights from feed stream 215 via first gaseous lights fraction 242 and toremove tars from feed stream 215 in distillation separator 240.

As stated above, low boiling component 244 recovered from separator 240includes the cis isomer of 1,3-dichloro-1-propene and also impurities,including alkenes and hydrogen chloride produced by the catalyticdehydrochlorination of tertiary chlorinated alkanes and/or tertiarychlorinated alkenes in reactor 220. Component 244, also referred to as“rough cis fraction 244,” is fed into second distillation separator 250,also referred to herein as the “cis distillation column” or “ciscolumn,” which is effective to purify the cis isomer of1,3-dichloro-1-propene present in fraction 244 by removing mid-boilingimpurities 256 from the bottom of separator 250 and removing secondgaseous lights fraction 252 from the top of separator 250. As used inconnection with separator 250 of this embodiment, the term “mid-boilingimpurities” refers to compounds having boiling points higher than theboiling point of the cis isomer of 1,3-dichloro-1-propene, which midboiling impurities can be separated from the cis isomer by accumulatingin the bottom of separator 250. Purified cis-1,3-dichloro-1-propene 254is recovered from second distillation separator 250.

Second distillation separator 250, like separator 50 in FIG. 1, can be aconventional distillation column, can have a configuration as describedabove in connection with separator 50, and can be operated at similardistillation temperatures and pressures as described above in connectionwith separator 50. In alternate embodiments, second distillationseparator 250 can be set up for use in a batch distillation system or acontinuous distillation system.

Purified trans-1,3-dichloro-1-propene 246 and purifiedcis-1,3-dichloro-1-propene 254 are then fed to mixer 260, where they aremixed in predetermined proportions to provide product 264, such as, forexample, a more highly purified Telone II® product. In otherembodiments, purified trans-1,3-dichloro-1-propene 246 and purifiedcis-1,3-dichloro-1-propene 254 are not mixed, but are instead used,sold, shipped or stored separately.

System 210 can also include optional liquid recirculation loop 221, asdepicted in FIG. 4, to enhance the yield of the dehydrochlorinationreaction. Optional liquid recirculation loop 221 includes flow path 223for extracting a portion of the distilling mixture from a position inseparator 240 beneath reactor 220 and flow path 227 for returning thedistilling mixture to a position in separator 240 above reactor 220,using pump 225. Optional' recirculation loop, when present, provides anopportunity for any tertiary chlorinated alkane and/or tertiarychlorinated alkene impurities that may have passed through reactor 220without being converted to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride to pass again throughreactor 220, thereby providing a further opportunity for conversion bydehydrochlorination, and ultimately increasing the purity of product264.

System 310 depicted in FIG. 5 includes reactor 320 positioned withinsecond distillation separator 350. In this embodiment, reactor 320 canbe a packed bed reactor or can comprise baffles or other structures thatare made of the catalytic material and that are positioned within seconddistillation separator 350.

In operation of the system set forth in FIG. 5, feed stream 315 is fedinto first distillation separator 340, which, like separator 40 in FIG.1, can be a conventional distillation column, can have a configurationas described above in connection with separator 40, and can be operatedat similar distillation temperatures and pressures as described above inconnection with separator 40. In alternate embodiments, firstdistillation separator 340 can be set up for use in a batch distillationsystem or a continuous distillation system.

First distillation separator 340 is effective to separate and purify thehigher boiling trans isomer of 1,3-dichloro-1-propene by removing a lowboiling component 344 containing the cis isomer and impurities from thetop of separator 340 and recovering purifiedtrans-1,3-dichloro-1-propene 346 from separator 340 as a high boilingcomponent. Tertiary chlorinated alkane and/or tertiary chlorinatedalkene impurities present in feed stream 315 separate with cis isomercomponent 344. In a case where feed stream 315 includes other lowboiling other components, such as, for example, C₃ compounds or otherlow boiling components, these are separated and recovered together withthe cis-isomer in low boiling component 344 or as first gaseous lightsfraction 342. Separator 340 is also effective to separate tar fraction348, which can be recovered from the bottom of separator 340.

Low boiling component 344 recovered from separator 340, which includesthe cis isomer of 1,3-dichloro-1-propene and also impurities, includingtertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities, is fed into second distillation separator 350 (cis column),which has reactor 320 positioned therein. Separator 350 is effective toseparate and purify the lower boiling cis isomer of1,3-dichloro-1-propene while at the same time converting tertiarychlorinated alkane and/or tertiary chlorinated alkene impurities incomponent 344 to corresponding unchlorinated or less-chlorinated alkenesand hydrogen chloride. Purified cis-1,3-dichloro-1-propene is separatedand recovered in separator 350 by removing mid-boiling impurities 356from the bottom of separator 350 and removing second gaseous lightsfraction 352 from the top of separator 350. The newly generated alkenesand hydrogen chloride produced by the catalyzed reaction of tertiarychlorinated alkane and/or tertiary chlorinated alkene impurities inreactor 320, are recovered from the top of separator 350 in secondgaseous lights fraction 352.

In the purification scheme described in connection with FIG. 5, seconddistillation separator 350, like separator 50 in FIG. 1, can be aconventional distillation column, can have a configuration as describedabove in connection with separator 50, and can be operated at similardistillation temperatures and pressures as described above in connectionwith separator 50, with the proviso that separator 350 is modified toinclude therein reactor 320, which can comprise, for example, a packedbed of sorbent-type catalyst particles or, alternatively, baffles madeof sorbent-type catalyst materials. In alternate embodiments, firstdistillation separator 350 can be set up for use in a batch distillationsystem or a continuous distillation system.

Purified trans-1,3-dichloro-1-propene 346 and purifiedcis-1,3-dichloro-1-propene 354 are then fed to mixer 360, where they aremixed in predetermined proportions to provide product 364, such as, forexample, a more highly purified Telone II® product. In otherembodiments, purified trans-1,3-dichloro-1-propene 346 and purifiedcis-1,3-dichloro-1-propene 354 are not mixed, but are instead used,sold, shipped or stored separately.

System 310 can also include optional liquid recirculation loop 321, asdepicted in FIG. 6, to enhance the progress of the dehydrochlorinationreaction. Optional liquid recirculation loop 321 includes flow path 323for extracting a portion of the distilling mixture from a position inseparator 350 beneath reactor 320 and flow path 327 for returning thedistilling mixture to a position in separator 350 above reactor 320,using pump 325. Optional recirculation loop, when present, provides anopportunity for any tertiary chlorinated alkane and/or tertiarychlorinated alkene impurities that may have passed through reactor 320without being converted to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride to pass again throughreactor 320, thereby providing a further opportunity for conversion bydehydrochlorination, and ultimately increasing the purity of product364.

Systems 410 and 510 depicted in FIGS. 7 and 8, respectively, includefirst distillation separators 440, 540, which, like separator 40 in FIG.1, can be conventional distillation columns, can have configurations asdescribed above in connection with separator 40, and can be operated atsimilar distillation temperatures and pressures as described above inconnection with separator 40. In alternate embodiments, firstdistillation separators 440, 540 can be set up for use in a batchdistillation system or a continuous distillation system. Systems 410 and510 also include second distillation separators 450, 550, which, likeseparator 50 in FIG. 1, can be a conventional distillation column, canhave a configuration as described above in connection with separator 50,and can be operated at similar distillation temperatures and pressuresas described above in connection with separator 50. In alternateembodiments, second distillation separators 450, 550 can be set up foruse in a batch distillation system or a continuous distillation system.

System 410 depicted in FIG. 7, includes reactor circuit 421 configuredto extract distilling mixture from separator 440 (trans column), passthe distilling mixture in contact with a dehydrochlorination catalyst,and return the dehydrochlorination-treated distilling mixture intoseparator 440. More specifically, reactor circuit 421 includes flowstream 428, with pump 425, for extracting a portion of the distillingmixture from separator 440 and feeding the extracted distilling mixtureinto catalytic reactor 420 that defines a reaction chamber, where it iscontacted with a sorbent-type catalyst to convert tertiary chlorinatedalkane and/or tertiary chlorinated alkene impurities in flow stream 428to corresponding unchlorinated or less-chlorinated alkenes and hydrogenchloride.

Catalytic reactor 420 is also configured to receive optional strippinggas flow stream 422 and to pass a stripping gas through the reactionchamber, thereby removing reaction products in the vapor phase that areproduced in catalytic reactor 420. After passage through the reactionchamber of reactor 420, the stripping gas can then be processed toremove hydrogen chloride and other reaction products entrained therein.In other embodiments, stripping gas flow stream 422 is absent.

Reactor circuit 421 also includes return flow path 429 for returning thedehydrochlorination-treated distilling mixture to separator 440 forfurther distillation processing. As used herein, the term“dehydrochlorination-treated distilling mixture” refers to a mixturethat has been contacted with a dehydrochlorination catalyst as describedherein, and which includes a reduced amount of tertiary chlorinatedalkane and/or tertiary chlorinated alkene impurities compared to flowstream 428. As a result, rough cis fraction 444 separated and recoveredfrom separator 440 has a lower tertiary chlorinated alkane and/ortertiary chlorinated alkene content than it would have in the absence ofreactor circuit 421, and purified cis fraction 454 is in a more highlypurified form than would be produced in the absence of reactor circuit421.

System 510 depicted in FIG. 8, includes reactor circuit 521 configuredto extract distilling mixture from separator 550 (cis column), pass thedistilling mixture in contact with a dehydrochlorination catalyst, andreturn the dehydrochlorination-treated distilling mixture into separator550. More specifically, reactor circuit 521 includes flow stream 528,with pump 525, for extracting a portion of the distilling mixture fromseparator 550 and feeding the extracted distilling mixture intocatalytic reactor 520 that defines a reaction chamber, where it iscontacted with a sorbent-type catalyst to convert tertiary chlorinatedalkane and/or tertiary chlorinated alkene impurities in flow stream 528to corresponding unchlorinated or less-chlorinated alkenes and hydrogenchloride.

Catalytic reactor 520 is also configured to receive optional strippinggas flow stream 522 and to pass a stripping gas through the reactionchamber, thereby removing reaction products in the vapor phase that areproduced in catalytic reactor 520. After passage through the reactionchamber of reactor 520, the stripping gas can then be processed toremove hydrogen chloride and other reaction products entrained therein.In other embodiments, stripping gas flow stream 522 is absent.

Reactor circuit 521 also includes return flow path 529 for returning thedehydrochlorination-treated distilling mixture to separator 550 forfurther distillation processing. As used herein, the term“dehydrochlorination-treated distilling mixture” refers to a mixturethat has been contacted with a dehydrochlorination catalyst as describedherein, and which includes a reduced amount of tertiary chlorinatedalkane and/or tertiary chlorinated alkene impurities compared to flowstream 528. As a result, purified cis fraction 554 has a lower tertiarychlorinated alkane and/or tertiary chlorinated alkene content than itwould have in the absence of reactor circuit 521.

In other embodiments, dehydrochlorination treatments as described hereincan be used in connection with purification schemes in which the ciscolumn precedes the trans column in the distillation process. Forexample, with reference to FIG. 9, system 610 includes catalytic reactor620 and vapor liquid separator and cooler 630 similar to catalyticreactor 20 and vapor liquid separator and cooler 30 described above inconnection with system 10 depicted in FIG. 1. However, first liquidfraction 634 recovered from vapor liquid separator and cooler 634 is notfed into a trans column as is first liquid fraction 34 depicted inFIG. 1. Rather, first liquid fraction 634 is fed into cis column 650,which is effective to purify the cis isomer of 1,3-dichloro-1-propenepresent in first liquid fraction 634 into fraction 654 recovered fromseparator 650, removing mid-boiling impurities 656 from a lower positionof separator 650, removing first gaseous lights fraction 652 from thetop of separator 650, and collecting rough trans-1,3-dichloro-1-propenefraction 658 from the bottom of separator 650. As used in connectionwith this embodiment, the term “mid-boiling impurities” refers tocompounds having boiling points higher than the boiling point of the cisisomer of 1,3-dichloro-1-propene and lower than the boiling point of thetrans isomer of 1,3-dichloro-1-propene, which can be separated from thecis and trans isomers from a lower position of separator 650. In oneembodiment, cis column 650 is operated at a temperature slightly belowthe boiling point of the trans isomer of 1,3-dichloro-1-propene andabove the boiling point of the cis isomer of 1,3-dichloro-1-propene.

Rough trans-1,3-dichloro-1-propene fraction 658 is then fed into transcolumn 640, which is effective to separate and purify the higher boilingtrans isomer of 1,3-dichloro-1-propene by removing a mid boiling andlights component 642 containing impurities from the top of trans column640 and recovering purified trans-1,3-dichloro-1-propene 646 from column640 as a high boiling component. Column 640 also separates tar fraction648, which can be recovered from the bottom of column 640.

Purified trans-1,3-dichloro-1-propene 646 and purifiedcis-1,3-dichloro-1-propene 654 are then fed to mixer 660, where they aremixed in predetermined proportions to provide product 664, such as, forexample, a more highly purified Telone II® product. In otherembodiments, purified trans-1,3-dichloro-1-propene 646 and purifiedcis-1,3-dichloro-1-propene 654 are not mixed, but are instead used,sold, shipped or stored separately.

In still other embodiments, dehydrochlorination treatments as describedherein can be used in connection with purification schemes in which thecis and trans distillation processes are conducted in a single dividingwall column. For example, with reference to FIG. 10, system 710represents a system in which dehydrochlorination is performed prior todistillation in dividing wall distillation column 771. In system 710,feed stream 715 is fed into catalytic reactor 720 that defines areaction chamber, where it is contacted with a sorbent-type catalyst toconvert tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities in feed stream 715 to corresponding unchlorinated orless-chlorinated alkenes and hydrogen chloride. The reaction of tertiarychlorinated alkanes and/or tertiary chlorinated alkenes is carried outat a temperature and pressure, and under conditions similar to thosedescribed above in connection with reactor 20 of FIG. 1. Catalyticreactor 720 is also configured to receive optional stripping gas flowstream 722 and to pass the stripping gas through the reaction chamber,thereby removing reaction products in the vapor phase that are producedin catalytic reactor 720. After passage through the reaction chamber ofreactor 720, the stripping gas can then be processed to remove hydrogenchloride and other reaction products entrained therein. In otherembodiments, stripping gas flow stream 722 is absent.

Reaction zone effluent 724 (also referred to herein as “phase 2 reactionmixture 724”), which exits reactor 720, includes a reduced amount oftertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities compared to component feed stream 715. Reaction zone effluentis then conveyed to vapor liquid separator and cooler 730 to separatecomponents of reaction zone effluent 724 into first gaseous lightsfraction 732 and distillation feed mixture 734, which includes cis- andtrans-1,3-dichloropropene and distillable impurities.

Distillation feed mixture 734 is then fed into dividing walldistillation column 770. Column 770 can be of a type commerciallyavailable and known to persons of ordinary skill in the art. Briefly,column 770 includes internal barrier 771 that divides column into twodistillation chambers. Column 770 is effective for separatingdistillation feed mixture 734 into multiple fractions. Specifically withreference to system 710, column 770 is effective to separatedistillation feed mixture 734 into purified cis-1,3-dichloro-1-propenefraction 774 and purified trans-1,3-dichloro-1-propene fraction 779,while separating same from second lights fraction 772, mid-boilingimpurity fraction 776 and tars fraction 778. Second lights fraction 772,mid-boiling impurity fraction 776 and tars fraction 778 can be disposedof via any conventional means.

Purified trans-1,3-dichloro-1-propene fraction 779 and purifiedcis-1,3-dichloro-1-propene fraction 774 are then fed to mixer 760, wherethey are mixed in predetermined proportions to provide a purified finalproduct 764 that is useful as a pesticide, such as, for example, apurified Telone II® product. In other embodiments, purifiedtrans-1,3-dichloro-1-propene fraction 779 and purifiedcis-1,3-dichloro-1-propene fraction 774 are not mixed, but are insteadused, sold, shipped or stored separately.

FIG. 11 depicts another embodiment in which a single dividing wallcolumn is used; however, in system 810, dehydrochlorination is performedafter distillation in the dividing wall column. Because tertiarychlorinated alkane and/or tertiary chlorinated alkene impurities tend toseparate with the cis fraction, this embodiment featuresdehydrochlorination treatment of the cis fraction after separation individing wall column 870. More specifically, feed stream 815 is fed intodividing wall distillation column 870, which is effective to divide feedstream 815 into fraction 874, which includes cis-1,3-dichloro-1-propeneand tertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities, and purified trans-1,3-dichloro-1-propene fraction 879.Fractions 874 and 879 are thus separated from first lights fraction 872,mid-boiling impurity fraction 876 and tars fraction 878. Column 870,like column 770 in FIG. 10, includes internal barrier 871 that dividescolumn into two distillation chambers, can have a configuration asdescribed above in connection with column 770, and can be operated atsimilar distillation temperatures and pressures as described above inconnection with column 770. In alternate embodiments, dividing wallcolumn 870 can be set up for use in a batch distillation system or acontinuous distillation system. Second lights fraction 872, mid-boilingimpurity fraction 876 and tars fraction 878 can be disposed of via anyconventional means.

As stated above, tertiary chlorinated alkane and/or tertiary chlorinatedalkene impurities present in feed stream 815 separate with the cisisomer in fraction 874. Fraction 874 is fed into a reaction chamber ofcatalytic reactor 820, where it is contacted with a sorbent-typecatalyst to convert tertiary chlorinated alkane and/or tertiarychlorinated alkene impurities in fraction 874 to correspondingunchlorinated or less-chlorinated alkenes and hydrogen chloride. Thereaction of tertiary chlorinated alkane and/or tertiary chlorinatedalkene impurities is carried out at a temperature and pressure, andunder conditions similar to those described above in connection withreactor 20. Catalytic reactor 820 is also configured to receive optionalstripping gas flow stream 822 and to pass the stripping gas through thereaction chamber, thereby removing reaction products in the vapor phasethat are produced in catalytic reactor 820. After passage through thereaction chamber of reactor 820, the stripping gas can then be processedto remove hydrogen chloride and other reaction products entrainedtherein. Reaction zone effluent 824 (also referred to herein as “phase 2reaction mixture 824”) exiting reactor 820 includes a reduced amount oftertiary chlorinated alkane and/or tertiary chlorinated alkeneimpurities compared to fraction 874. Reaction zone effluent 824 is thenconveyed to vapor liquid separator and cooler 830 to separate reactionzone effluent 824 into first gaseous lights fraction 832 and rough cisfraction 834, which includes cis-1,3-dichloropropene and distillableimpurities.

Rough cis fraction 834 is then fed into second distillation separator880, also referred to herein as the “lights column,” which is effectiveto purify the cis isomer of 1,3-dichloro-1-propene present in fraction834 by removing mid-boiling impurities 888 from the bottom of separator880 and removing third gaseous lights fraction 882 from the top ofseparator 880. As used in connection with separator 880 of thisembodiment, the term “mid-boiling impurities” refers to compounds havingboiling points higher than the boiling point of the cis isomer of1,3-dichloro-1-propene, which can be separated from the cis isomer byaccumulating in the bottom of separator 880. Purifiedcis-1,3-dichloro-1-propene 884 is recovered from second distillationseparator 880.

Second distillation separator 880, like separator 50 in FIG. 1, can be aconventional distillation column, can have a configuration as describedabove in connection with separator 50, and can be operated at similardistillation temperatures and pressures as described above in connectionwith separator 50. In alternate embodiments, second distillationseparator 880 can be set up for use in a batch distillation system or acontinuous distillation system.

Purified trans-1,3-dichloro-1-propene fraction 879 and purifiedcis-1,3-dichloro-1-propene fraction 884 are then fed to mixer 860, wherethey are mixed in predetermined proportions to provide purified product864, such as, for example, a more highly purified Telone II® product. Inother embodiments, purified trans-1,3-dichloro-1-propene fraction 879and purified cis-1,3-dichloro-1-propene fraction 884 are not mixed, butare instead used, sold, shipped or stored separately.

By the processes described herein, both the cis-isomer and thetrans-isomer of 1,3-dichloro-1-propene can be obtained at high puritylevels, such as, for example, at purity levels of at least 98%, morepreferably at least 99%. Specifically, the impurity2-chloro-2-methylpentane commonly present in Telone crude can be reducedto a level below 1000 ppm, the impurity 2-chloro-2,3-dimethylbutanecommonly present in Telone crude can be reduced to a level below 1000ppm and the impurity 4-chloro-4-methyl-1-pentene commonly present inTelone crude can be reduced to levels below 1000 ppm. Indeed, impuritylevels can be reduced to significantly lower than 1000 ppm usingtechniques described herein. The cis-isomer and the trans-isomerobtained by the processes described here can be used, for example, assoil fumigants to control nematodes.

In addition to the embodiments depicted in FIGS. 1-11, the presentapplication contemplates that additional unit processes can be added tothe system as would occur to a person skilled in the art. For exampleand without limitation, when feed stream 15, 115, 215, 315, 415, 515,615, 715, 815 comprises Telone crude or a similarly composed mixture, itmay be desirable to subject the feed stream to a chlorination treatmentprior to feeding the feed stream into a reactor or distillation columnin accordance with the various embodiments. Additional optionaltreatment phases can include, for example, a primary tar removaltreatment, which can be performed either before or after catalyticdehydrochlorination treatment, but preferably before distillationtreatment; and/or a propane dichloride removal and purificationtreatment, which preferably occurs before catalytic dehydrochlorinationtreatment and before distillation treatment.

It is well known that before a pesticide can be used or soldcommercially, such pesticide undergoes lengthy evaluation processes byvarious governmental authorities (local, regional, state, national,international). Voluminous data requirements are specified by regulatoryauthorities and must be addressed through data generation and submissionby the product registrant or by another on the product registrant'sbehalf. These governmental authorities then review such data and if adetermination of safety is concluded, provide the potential user orseller with product registration approval. Thereafter, in that localitywhere the product registration is granted and supported, such user orseller may use or sell such pesticide. In another aspect of the presentapplication, therefore, there is provided a process that includessubmitting data to a governmental authority in order to obtain productregistration approval for a product comprising a purifiedcis-1,3-dichloro-1-propene fraction made in accordance with theprocesses of the present application, a purifiedtrans-1,3-dichloro-1-propene fraction made in accordance with theprocesses of the present application or a purified1,3-dichloro-1-propene mixture made in accordance with the processes ofthe present application

Many other aspects and embodiments are also envisioned. For example, asa closing observation, the various processes of FIGS. 1-11 have beendescribed particularly with regard to processes for removing tertiarychlorinated alkane and/or tertiary chlorinated alkene impurities from afeed stream including 1,3-dichloro-1-propene as a major component. Thoseskilled in the art will however readily appreciate that the processes ofFIGS. 1-11 and the concepts embodied therein are more broadly applicableto the removal of tertiary halogenated hydrocarbon impurities from awide variety of hydrocarbon compounds, and are especially applicable tothe removal of tertiary halogenated hydrocarbon impurities from otherhalogenated hydrocarbons and/or from hydrocarbons having boiling pointssimilar to (e.g., within about 5° C. of) one or more of the tertiaryhalogenated hydrocarbon impurities. Because the catalyzeddehydrohalogenation reactions described herein are selective fortertiary halogenated hydrocarbons having a beta hydrogen, the methodsand systems described herein lend themselves well to the selectiveremoval of tertiary halogenated hydrocarbons from other halogenatedhydrocarbons.

As will be appreciated by a person skilled in the art in view of theabove descriptions, in one aspect of the present application, there isprovided a method for removing a tertiary chlorinated hydrocarbonimpurity from 1,3-dichloro-1-propene that includes: (1) providing afirst mixture comprising 1,3-dichloro-1-propene and a tertiarychlorinated hydrocarbon impurity; (2) contacting the first mixturecontaining the tertiary chlorinated hydrocarbon impurity with adehydrochlorination catalyst effective to catalyze a conversion of thetertiary chlorinated hydrocarbon impurity to a correspondingunchlorinated or less-chlorinated unsaturated hydrocarbon and hydrogenchloride; and (3) distilling the 1,3-dichloro-1-propene to separate andrecover a purified cis-1,3-dichloro-1-propene fraction and a purifiedtrans-1,3-dichloro-1-propene fraction. The purifiedcis-1,3-dichloro-1-propene fraction and the purifiedtrans-1,3-dichloro-1-propene fraction can optionally then be mixed in apredetermined ratio to provide a purified 1,3-dichloro-1-propenemixture. In one embodiment, first mixture containing the tertiarychlorinated hydrocarbon impurity is contacted with a dehydrochlorinationcatalyst by providing a reactor defining a reaction zone containing thecatalyst and feeding the first mixture containing the tertiarychlorinated hydrocarbon impurity into the reaction zone in contact withthe catalyst. In another embodiment, a stripping gas stream is alsopassed through the reaction zone. The tertiary chlorinated hydrocarboncan be, for example, a tertiary chlorinated alkane having a betahydrogen or a tertiary chlorinated alkene having a beta hydrogen. Thedehydrochlorination catalyst can be, for example, activated alumina,sintered alumina, activated clay, fumed silica or silica gel, ormagnesium silicate. Alternatively, the dehydrochlorination catalyst canbe, for example, TiO₂, Al₂O₃, ZrO₂, AlPO₄ or Al_(x)Si_(y)O_(z), or oneof these materials doped with a metal.

One embodiment comprises: first contacting the first mixture containingthe tertiary chlorinated hydrocarbon with the dehydrochlorinationcatalyst to produce a second mixture comprising 1,3-dichloro-1-propeneand the corresponding unchlorinated or less-chlorinated unsaturatedhydrocarbon; and then distilling the second mixture to produce apurified cis-1,3-dichloro-1-propene fraction and a purifiedtrans-1,3-dichloro-1-propene fraction. The distilling can include, forexample: (1) feeding the second mixture into a first distillationseparator; (2) recovering from the first distillation separator thepurified trans-1,3-dichloro-1-propene fraction, a rough cis fraction, asecond lights fraction and a tars fraction; (3) feeding the rough cisfraction into a second distillation separator; and (4) recovering fromthe second distillation separator the purifiedcis-1,3-dichloro-1-propene fraction, a third lights fraction and amid-boiling impurities fraction. In another example, the distillingincludes: (1) feeding the second mixture into a first distillationseparator; (2) recovering from the first distillation separator thepurified cis-1,3-dichloro-1-propene fraction, a roughtrans-1,3-dichloro-1-propene fraction, a second lights fraction and amid-boiling impurities fraction; (3) feeding the roughtrans-1,3-dichloro-1-propene fraction into a second distillationseparator; and (4) recovering from the second distillation separator thepurified trans-1,3-dichloro-1-propene fraction, a third lights fractionand a tars fraction. In this example, the second distillation separatoris also effective to separate mid-boiling compounds in roughtrans-1,3-dichloro-1-propene fraction into third lights fraction. In yetanother example, the distilling includes: (1) feeding the second mixtureinto a dividing wall column distillation separator; and (2) recoveringfrom the separator the purified cis-1,3-dichloro-1-propene fraction, thepurified trans fraction, a second lights fraction, a mid-boilingimpurities fraction and a tars fraction.

In still another embodiment, the method includes: (1) distilling thefirst mixture containing the tertiary chlorinated hydrocarbon to producea purified trans-1,3-dichloro-1-propene fraction and acis-1,3-dichloro-1-propene fraction, the cis-1,3-dichloro-1-propenefraction including the tertiary chlorinated hydrocarbon impurity; (2)contacting the cis-1,3-dichloro-1-propene fraction containing thetertiary chlorinated hydrocarbon with the dehydrochlorination catalystto produce a second mixture (phase 2 mixture) comprisingcis-1,3-dichloro-1-propene and the corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon; and (3) distilling the secondmixture to produce a purified cis-1,3-dichloro-1-propene fraction. Inone example, the distilling the first mixture containing the tertiarychlorinated hydrocarbon comprises feeding the first mixture into adividing wall column distillation separator and recovering from thedividing wall column distillation separator the purifiedcis-1,3-dichloro-1-propene fraction, the purified trans fraction, afirst lights fraction, a mid-boiling impurities fraction and a tarsfraction; the contacting comprises feeding thecis-1,3-dichloro-1-propene fraction containing the tertiary chlorinatedhydrocarbon impurity into a reactor defining a reaction zone containingthe catalyst to produce the second mixture; and the distilling thesecond mixture comprises feeding the second mixture into a secondseparator and recovering from the second separator the purifiedcis-1,3-dichloro-1-propene, a second lights fraction and a mid-boilingimpurities fraction. The method can also optionally include passing astripping gas stream through the reaction zone.

A further embodiment includes: (1) distilling the first mixturecontaining the tertiary chlorinated hydrocarbon impurity to produce apurified trans-1,3-dichloro-1-propene fraction and acis-1,3-dichloro-1-propene fraction, the cis-1,3-dichloro-1-propenefraction including at least one impurity; and (2) distilling thecis-1,3-dichloro-1-propene fraction containing the at least one impurityto produce a purified cis-1,3-dichloro-1-propene fraction. In thisembodiment, the distilling the first mixture containing the tertiarychlorinated hydrocarbon impurity comprises feeding the first mixtureinto a distillation separator defining a distillation chamber, saiddistillation chamber having the dehydrochlorination catalyst positionedtherein. In yet another variation of this embodiment, the distillationseparator further comprises a recirculation loop configured to extract afluid from the distillation chamber at a position below thedehydrochlorination catalyst and to return the fluid to the distillationchamber at a position above the dehydrochlorination catalyst.

Yet a further embodiment comprises: (1) distilling the first mixturecontaining the tertiary chlorinated hydrocarbon impurity to produce apurified trans-1,3-dichloro-1-propene fraction and a roughcis-1,3-dichloro-1-propene fraction, the roughcis-1,3-dichloro-1-propene fraction including at least one impurity; and(2) distilling the rough cis-1,3-dichloro-1-propene fraction to producea purified cis-1,3-dichloro-1-propene fraction. In this embodiment,distilling the rough cis-1,3-dichloro-1-propene fraction comprisesfeeding the rough cis-1,3-dichloro-1-propene fraction into adistillation separator defining a distillation chamber, the distillationchamber having the dehydrochlorination catalyst positioned therein. Inyet another variation of this embodiment, the distillation separatorfurther comprises a recirculation loop configured to extract a fluidfrom the distillation chamber at a position below thedehydrochlorination catalyst and to return the fluid to the distillationchamber at a position above the dehydrochlorination catalyst.

Yet another embodiment is directed to a method that includes: (1)distilling the first mixture containing the tertiary chlorinatedhydrocarbon impurity in a first distillation separator to produce apurified trans-1,3-dichloro-1-propene fraction and a roughcis-1,3-dichloro-1-propene fraction, the roughcis-1,3-dichloro-1-propene fraction including at least one impurity; (2)distilling the rough cis-1,3-dichloro-1-propene fraction in a seconddistillation separator to produce a purified cis-1,3-dichloro-1-propenefraction; (3) extracting a portion of a distilling mixture from thefirst distillation separator, the distilling mixture including at leasta portion of the tertiary chlorinated hydrocarbon impurity; (4)contacting the distilling mixture with a dehydrochlorination catalysteffective to catalyze a conversion of the tertiary chlorinatedhydrocarbon impurity in the distilling mixture to a correspondingunchlorinated or less-chlorinated unsaturated hydrocarbon and hydrogenchloride, thereby producing a dehydrochlorination-treated distillingmixture; and (5) returning the dehydrochlorination-treated distillingmixture to the first distillation separator.

Still another embodiment is directed to a method that includes: (1)distilling the first mixture containing the tertiary chlorinatedhydrocarbon impurity in a first distillation separator to produce apurified trans-1,3-dichloro-1-propene fraction and acis-1,3-dichloro-1-propene fraction, the cis-1,3-dichloro-1-propenefraction including at least one impurity; (2) distilling thecis-1,3-dichloro-1-propene fraction in a second distillation separatorto produce a purified cis-1,3-dichloro-1-propene fraction; (3)extracting a portion of a distilling mixture from the seconddistillation separator, the distilling mixture including at least aportion of the tertiary chlorinated hydrocarbon impurity; (4) contactingthe distilling mixture with a dehydrochlorination catalyst effective tocatalyze a conversion of the tertiary chlorinated hydrocarbon impurityin the distilling mixture to a corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon and hydrogen chloride, therebyproducing a dehydrochlorination-treated distilling mixture; and (5)returning the dehydrochlorination-treated distilling mixture to thesecond distillation separator.

In another aspect of the present application, there is provided a methodfor removing a tertiary halogenated hydrocarbon impurity from a targethydrocarbon compound that includes: (1) providing a first mixturecomprising a target hydrocarbon compound and a tertiary halogenatedhydrocarbon impurity; (2) contacting the first mixture containing thetertiary halogenated hydrocarbon impurity with a dehydrohalogenationcatalyst effective to catalyze a conversion of the tertiary halogenatedhydrocarbon impurity to a corresponding unhalogenated orless-halogenated unsaturated hydrocarbon and hydrogen halide, therebyproviding a modified mixture; and (3) distilling the modified mixture toseparate and recover a purified target hydrocarbon compound.

In yet another aspect, the application provides a method fordehydrohalogenating a tertiary halogenated hydrocarbon that includes:(1) providing a catalytic reactor defining a reaction chamber, thereaction chamber containing a sorbent-type dehydrohalogenation catalysteffective to catalyze a reaction of a tertiary halogenated hydrocarbonto a corresponding unhalogenated or less halogenated unsaturatedhydrocarbon; (2) conveying a fluid comprising a tertiary halogenatedhydrocarbon into the reaction chamber and into contact with the catalystto convert at least a portion of the tertiary halogenated hydrocarbon toa corresponding unhalogenated or less-halogenated unsaturatedhydrocarbon and hydrogen halide; and (3) passing a stripping gas throughthe reaction chamber to remove at least a portion of the hydrogen halidefrom the reaction chamber.

In still another aspect of the application, there is provided a processthat includes submitting data to a governmental authority in order toobtain product registration approval for a product that includes any oneof the purified cis-1,3-dichloro-1-propene fractions described herein,any one of the purified trans-1,3-dichloro-1-propene fractions describedherein, any one of the purified 1,3-dichloro-1-propene mixturesdescribed herein or any one of the purified target hydrocarbonsdescribed herein.

Reference will now be made to the following Examples, which describeexperimental work directed to the subject matter of the presentapplication. It is understood that no limitation to the scope of theapplication is intended thereby. The Examples are intended to beillustrative, are provided solely to promote a full understanding of theconcepts embodied in the application, and are not intended to belimiting or otherwise restrictive as to the nature and scope of theinventions set forth herein.

Examples Example One Batch Experiments

Experiment I

In a first set of experiments, at ambient temperature, approximately 3ml of Telone II® was loaded on top of 0.3 g of various solidsorbent-type catalysts. The vials were shaken for 48 hours at roomtemperature, then sampled and analyzed by gas chromatography with aflame ionization detector. When compared to the starting Telone IIsample, the material that was contacted with silicon oxide and aluminumoxide containing solids showed a substantial (i.e., up to 100%)reduction in concentration in the tertiary chlorinated alkanes andalkenes and an increase in their decomposition products. Carbon basedadsorbents showed a negligible reduction in chlorinated alkaneconcentration.

Experiment II

A second set of batch tests focused on the aluminum and silicone oxidecatalysts and repeated the procedure of Experiment I. Each vial wassampled and the samples analyzed by gas chromatography with a flameionization detector after one, three and 24 hours to understand thereaction as a function of time. In a follow-up, the process was repeatedwith the used catalyst and fresh Telone II®. Both experiments showedsignificant reductions in tertiary chlorinated alkanes and alkenes withmost of the silicon and aluminum adsorbents. It was discovered that thepH of the catalyst has an effect on the rate of the reaction.

Experiment III

The same procedure as Experiment II was repeated at 60° C. but over amuch shorter time frame. Each vial was sampled and analyzed after 15, 45and 180 minutes. The results showed an approximate doubling of the rateof reaction for every increase of 10° C.

Example Two Reaction Flow Tests

A packed bed reactor was constructed to test the effects of continuousflow across a catalyst bed. The reactor consisted of a ¼″ OD tube loadedwith catalyst. The exterior of the tube was jacketed with a recirculatedheating fluid providing an isothermal temperature zone across thereactor. The feed was pumped into the reactor in upflow mode, with theoption to add an inert gas flow before entering the reactor.

Experiment I

Approximately 3 grams of F-200 activated alumina catalyst were loaded inthe reactor and Telone II® (with tertiary chlorinated hydrocarbonsranging from 950 to 2550 ppm) was fed at 1 mL/min. The reactor wasmaintained at 90° C. without nitrogen flow. The initial results showed astable reduction of about 12-21% for the tertiary chlorinatedhydrocarbons after the reaction.

Experiment II

The reactor was again loaded with 3 grams of F-200 activated alumina,with a liquid feed of 1 mL/min of Telone II®. For this experiment, 10standard cubic centimeters per minute (sccm) of nitrogen was also addedto the reactor at 90° C. In this case, the conversion of the tertiarychlorinated hydrocarbons was increased to 45-55%

Experiment III

With the same set-up described in experiment II, the temperature in thereactor was increased to 105° C., leaving the liquid flow rate at 1mL/min and the gas flow rate at 10 sccm of nitrogen. The conversion ofthe tertiary chlorinated hydrocarbons increased to 75-95%.

Experiment IV

Three grams of silica gel (60-200 mesh, 100 Angstrom pore diameter) wasloaded into the reactor. The catalyst was at 1 mL/min Telone II® flow,10 sccm nitrogen, reactor pressure of 25 psia, and at a reactiontemperature of 125° C. The tertiary chlorinated hydrocarbon conversionranged from 52 to 63% conversion under these conditions.

Experiment V

Experiments were performed over three grams of sintered aluminacatalyst. In this case, the feed was composed of a high puritycis-1,3-dichloropropene stream with approximately 3500 ppm of tertiarychlorinated hydrocarbons present. The liquid feed flow rate was 0.25mL/min and the nitrogen flow rate was 5 sccm. The steady-stateconversion was approximately 85% after 6 hours on stream.

Example Three Distillation and Reaction in Combination

Telone II® product was split into cis and trans fractions and furtherpurified using an industrial scale distillation column in the Telone IIproduction plant. As single isomer products are normally produced inthis column, the only variation from the standard operation was toproduce higher purity by slowing the operation and increasing waste. Theresulting purified isomers batches were mixed to produce a 50/50 to60/40 mix of cis and trans isomers for feeding into the reactordescribed in the Reaction Flow Test section above. The reactorconditions were varied (temperature, stripping gas flow) such that2-chloro-2-methylpentane concentrations in the reactor effluent werereduced to below 1000 ppm from 1200-2000 ppm. This material was thenstripped of the reaction by-products (lights) in a 2″ diameter batchdistillation column.

While multiple embodiments of the invention have been illustrated anddescribed in detail in the drawings and foregoing description, the sameis to be considered as illustrative and not restrictive in character, itbeing understood that only the selected embodiments have been shown anddescribed and that all changes, modifications and equivalents that comewithin the spirit of the invention as defined herein or by any of thefollowing claims are desired to be protected. Any theory, mechanism ofoperation, proof, or finding stated herein is meant to further enhanceunderstanding of the present application and is not intended to make thepresent application in any way dependent upon such theory, mechanism ofoperation, proof, or finding. It should be understood that any use ofthe word preferable, preferably or preferred in the description aboveindicates that the feature so described may be more desirable, itnonetheless may not be necessary and embodiments lacking the same may becontemplated as within the scope of the invention, that scope beingdefined by the claims that follow. In reading the claims it is intendedthat when words such as “a,” “an,” “at least one,” “at least a portion”are used there is no intention to limit the claim to only one itemunless specifically stated to the contrary in the claim. Further, whenthe language “at least a portion” and/or “a portion” is used the itemmay include a portion and/or the entire item unless specifically statedto the contrary. All patents, patent applications, and publicationsreferences herein are hereby incorporated by reference, each in itsentirety.

1. A method for removing a tertiary chlorinated hydrocarbon impurityfrom 1,3-dichloro-1-propene, comprising: providing a first mixturecomprising 1,3-dichloro-1-propene and a tertiary chlorinated hydrocarbonimpurity; contacting the first mixture containing the tertiarychlorinated hydrocarbon impurity with a dehydrochlorination catalysteffective to catalyze a conversion of the tertiary chlorinatedhydrocarbon impurity to a corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon and hydrogen chloride; anddistilling the 1,3-dichloro-1-propene to separate and recover a purifiedcis-1,3-dichloro-1-propene fraction and a purifiedtrans-1,3-dichloro-1-propene fraction; wherein the tertiary chlorinatedhydrocarbon impurity comprises an impurity selected from the groupconsisting of 2-chloro-2-methylpentane, 2-chloro-2,3-dimethylbutane,4-chloro-4-methyl-1-pentene and mixtures thereof.
 2. The method inaccordance with claim 1, further comprising mixing the purifiedcis-1,3-dichloro-1-propene fraction and the purifiedtrans-1,3-dichloro-1-propene fraction in a predetermined ratio toprovide a purified 1,3-dichloro-1-propene mixture.
 3. The method inaccordance with claim 1 wherein said contacting comprises feeding thefirst mixture containing the tertiary chlorinated hydrocarbon impurityinto a reactor defining a reaction zone containing the catalyst.
 4. Themethod in accordance with claim 3 wherein the conversion is conducted ata temperature of from about 20 to about 130° C.
 5. The method inaccordance with claim 3 wherein the conversion is conducted at apressure of from about 5 to about 30 psia.
 6. The method in accordancewith claim 3 wherein the feed stream comprises a liquid mixture having aflow rate of from 0 to about 4000 hr-1 gas hourly space velocity (GHSV)or a gaseous mixture having a flow rate of from 0 to about 4000 weighthourly space velocity (WHSV).
 7. The method in accordance with claim 3,further comprising passing a stripping gas stream through the reactionzone.
 8. The method in accordance with claim 7: wherein said feedingcomprises feeding a flow stream comprising a liquid mixture includingthe tertiary chlorinated hydrocarbon impurity through the reaction zoneat a rate of from 0 to about 4000 weight hourly space velocity (WHSV) orfeeding a flow stream comprising a gaseous mixture including thetertiary chlorinated hydrocarbon impurity through the reaction zone at arate of from 0 to about 4000 hr-1 gas hourly space velocity (GHSV);wherein said contacting comprises contacting the mixture containing thetertiary chlorinated hydrocarbon impurity with the dehydrochlorinationcatalyst at a temperature of from about 20 to about 200° C. and at apressure of from about 0.5 to about 50 psia; and wherein said passingcomprises passing the stripping gas stream through the reaction zone ata rate of from 0 to about 4000 hr-1 gas hourly space velocity (GHSV). 9.The method in accordance with claim 8 wherein the tertiary chlorinatedhydrocarbon is present in the flow stream at a concentration of fromabout 100 to about 10,000 ppm.
 10. The method in accordance with claim 7wherein said stripping gas is effective to remove one or more vaporphase reaction products from the reaction zone.
 11. The method inaccordance with claim 10, further comprising recovering at least one ofthe one or more vapor phase reaction products from the stripping gas.12. The method in accordance with claim 7 wherein the stripping gas isselected from the group consisting of nitrogen gas, helium gas, argongas, light hydrocarbon.
 13. The method in accordance with claim 1wherein the dehydrochlorination catalyst comprises a sorbent-typedehydrohalogenation catalyst selected from the group consisting ofactivated alumina, sintered alumina, activated clay, fumed silica,silica gel, magnesium silicate, TiO₂, Al₂O₃, ZrO₂, AlPO₄,Al_(x)Si_(y)O_(z) and mixtures thereof.
 14. The method in accordancewith claim 13 wherein the dehydrochlorination catalyst is doped with ametal.
 15. The method in accordance with claim 1 wherein said methodcomprises: contacting the first mixture containing the tertiarychlorinated hydrocarbon impurity with the dehydrochlorination catalystto produce a second mixture comprising 1,3-dichloro-1-propene and thecorresponding unchlorinated or less-chlorinated unsaturated hydrocarbon;and distilling the second mixture to produce a purifiedcis-1,3-dichloro-1-propene fraction and a purifiedtrans-1,3-dichloro-1-propene fraction.
 16. The method in accordance withclaim 15, further comprising, before said distilling, passing the secondmixture through a vapor/liquid separator and cooler to separate a firstlights fraction from the second mixture.
 17. The method in accordancewith claim 15 wherein said distilling comprises: feeding the secondmixture into a first distillation separator; recovering from the firstdistillation separator the purified trans-1,3-dichloro-1-propenefraction, a rough cis fraction, a second lights fraction and a tarsfraction; feeding the rough cis fraction into a second distillationseparator; and recovering from the second distillation separator thepurified cis-1,3-dichloro-1-propene fraction, a third lights fractionand a mid-boiling impurities fraction.
 18. The method in accordance withclaim 15 wherein said distilling comprises: feeding the second mixtureinto a first distillation separator; recovering from the firstdistillation separator the purified cis-1,3-dichloro-1-propene fraction,a rough trans-1,3-dichloro-1-propene fraction, a second lights fractionand a mid-boiling impurities fraction; feeding the roughtrans-1,3-dichloro-1-propene fraction into a second distillationseparator; and recovering from the second distillation separator thepurified trans-1,3-dichloro-1-propene fraction, a third lights fractionand a tars fraction; wherein the second distillation separator is alsoeffective to separate mid-boiling compounds in roughtrans-1,3-dichloro-1-propene fraction into third lights fraction. 19.The method in accordance with claim 15 wherein said distillingcomprises: feeding the second mixture into a dividing wall columndistillation separator; and recovering from the separator the purifiedcis-1,3-dichloro-1-propene fraction, the purified trans fraction, asecond lights fraction, a mid-boiling impurities fraction and a tarsfraction.
 20. The method in accordance with claim 1 wherein said methodcomprises: distilling the first mixture containing the tertiarychlorinated hydrocarbon impurity to produce a purifiedtrans-1,3-dichloro-1-propene fraction and a cis-1,3-dichloro-1-propenefraction, the cis-1,3-dichloro-1-propene fraction including the tertiarychlorinated hydrocarbon impurity; contacting thecis-1,3-dichloro-1-propene fraction with the dehydrochlorinationcatalyst to produce a second mixture comprisingcis-1,3-dichloro-1-propene and the corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon; and distilling the secondmixture to produce a purified cis-1,3-dichloro-1-propene fraction. 21.The method in accordance with claim 20, wherein said distilling thefirst mixture containing the tertiary chlorinated hydrocarbon impuritycomprises feeding the first mixture into a dividing wall columndistillation separator and recovering from the dividing wall columndistillation separator the purified trans-1,3-dichloro-1-propenefraction, the cis-1,3-dichloro-1-propene fraction, a first lightsfraction, a mid-boiling impurities fraction and a tars fraction; whereinsaid contacting comprises feeding the cis-1,3-dichloro-1-propenefraction including the tertiary chlorinated hydrocarbon impurity into areactor defining a reaction zone containing the catalyst to produce thesecond mixture; and wherein said distilling the second mixture comprisesfeeding the second mixture into a second separator and recovering fromthe second separator the purified cis-1,3-dichloro-1-propene, a secondlights fraction and a mid-boiling impurities fraction.
 22. The method inaccordance with claim 21, further comprising passing a stripping gasstream through the reaction zone.
 23. The method in accordance withclaim 1 wherein said method comprises: distilling the first mixturecontaining the tertiary chlorinated hydrocarbon impurity to produce apurified trans-1,3-dichloro-1-propene fraction and acis-1,3-dichloro-1-propene fraction, the cis-1,3-dichloro-1-propenefraction including at least one impurity; and distilling thecis-1,3-dichloro-1-propene fraction to produce a purifiedcis-1,3-dichloro-1-propene fraction; wherein said distilling the firstmixture containing the tertiary chlorinated hydrocarbon impuritycomprises feeding the first mixture into a distillation separatordefining a distillation chamber, said distillation chamber having thedehydrochlorination catalyst positioned therein.
 24. The method inaccordance with claim 23 wherein the dehydrochlorination catalystcomprises a form selected from the group consisting of a packed-bedcatalyst reactor positioned within the distillation chamber and bafflesor other structures made of the catalyst positioned within thedistillation chamber.
 25. The method in accordance with claim 23 whereinthe distillation separator further comprises a recirculation loopconfigured to extract a fluid from the distillation chamber at aposition below the dehydrochlorination catalyst and to return the fluidto the distillation chamber at a position above the dehydrochlorinationcatalyst.
 26. The method in accordance with claim 1 wherein said methodcomprises: distilling the first mixture containing the tertiarychlorinated hydrocarbon impurity to produce a purifiedtrans-1,3-dichloro-1-propene fraction and a roughcis-1,3-dichloro-1-propene fraction, the roughcis-1,3-dichloro-1-propene fraction including at least one impurity; anddistilling the rough cis-1,3-dichloro-1-propene fraction to produce apurified cis-1,3-dichloro-1-propene fraction; wherein said distillingthe rough cis-1,3-dichloro-1-propene fraction comprises feeding thefirst mixture into a distillation separator defining a distillationchamber, said distillation chamber having the dehydrochlorinationcatalyst positioned therein.
 27. The method in accordance with claim 26wherein the dehydrochlorination catalyst comprises a form selected fromthe group consisting of a packed-bed catalyst reactor positioned withinthe distillation chamber and baffles or other structures made of thecatalyst positioned within the distillation chamber.
 28. The method inaccordance with claim 26 wherein the distillation separator furthercomprises a recirculation loop configured to extract a fluid from thedistillation chamber at a position below the dehydrochlorinationcatalyst and to return the fluid to the distillation chamber at aposition above the dehydrochlorination catalyst.
 29. The method inaccordance with claim 1 wherein said method comprises: distilling thefirst mixture containing the tertiary chlorinated hydrocarbon impurityin a first distillation separator to produce a purifiedtrans-1,3-dichloro-1-propene fraction and a roughcis-1,3-dichloro-1-propene fraction, the roughcis-1,3-dichloro-1-propene fraction including at least one impurity;distilling the rough cis-1,3-dichloro-1-propene fraction in a seconddistillation separator to produce a purified cis-1,3-dichloro-1-propenefraction; extracting a portion of a distilling mixture from the firstdistillation separator, the distilling mixture including at least aportion of the tertiary chlorinated hydrocarbon impurity; contacting thedistilling mixture with a dehydrochlorination catalyst effective tocatalyze a conversion of the tertiary chlorinated hydrocarbon impurityin the distilling mixture to a corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon and hydrogen chloride, therebyproducing a dehydrochlorination-treated distilling mixture; andreturning the dehydrochlorination-treated distilling mixture to thefirst distillation separator.
 30. The method in accordance with claim 1wherein said method comprises: distilling the first mixture containingthe tertiary chlorinated hydrocarbon impurity in a first distillationseparator to produce a purified trans-1,3-dichloro-1-propene fractionand a cis-1,3-dichloro-1-propene fraction, thecis-1,3-dichloro-1-propene fraction including at least one impurity;distilling the cis-1,3-dichloro-1-propene fraction in a seconddistillation separator to produce a purified cis-1,3-dichloro-1-propenefraction; extracting a portion of a distilling mixture from the seconddistillation separator, the distilling mixture including at least aportion of the tertiary chlorinated hydrocarbon impurity; contacting thedistilling mixture with a dehydrochlorination catalyst effective tocatalyze a conversion of the tertiary chlorinated hydrocarbon impurityin the distilling mixture to a corresponding unchlorinated orless-chlorinated unsaturated hydrocarbon and hydrogen chloride, therebyproducing a dehydrochlorination-treated distilling mixture; andreturning the dehydrochlorination-treated distilling mixture to thesecond distillation separator.
 31. A method for removing a tertiarychlorinated hydrocarbon impurity from 1,3-dichloro-1-propene,comprising: providing a first mixture comprising 1,3-dichloro-1-propeneand a tertiary chlorinated hydrocarbon impurity; contacting the firstmixture containing the tertiary chlorinated hydrocarbon impurity with adehydrochlorination catalyst effective to catalyze a conversion of thetertiary chlorinated hydrocarbon impurity to a correspondingunchlorinated or less-chlorinated unsaturated hydrocarbon and hydrogenchloride; and distilling the 1,3-dichloro-1-propene to separate andrecover a purified cis-1,3-dichloro-1-propene fraction and a purifiedtrans-1,3-dichloro-1-propene fraction.
 32. A method for removing atertiary halogenated hydrocarbon impurity from a target hydrocarboncompound, comprising: providing a first mixture comprising a targethydrocarbon compound and a tertiary halogenated hydrocarbon impurity;contacting the first mixture containing the tertiary halogenatedhydrocarbon impurity with a dehydrohalogenation catalyst effective tocatalyze a conversion of the tertiary halogenated hydrocarbon impurityto a corresponding unhalogenated or less-halogenated unsaturatedhydrocarbon and hydrogen halide, thereby providing a modified mixture;and distilling the modified mixture to separate and recover a purifiedtarget hydrocarbon compound.
 33. The method in accordance with claim 32wherein the tertiary halogenated hydrocarbon has a boiling point within5° C. of the boiling point of the target hydrocarbon compound.
 34. Themethod in accordance with claim 32 wherein the target hydrocarboncompound comprises a halogenated hydrocarbon compound.
 35. The method inaccordance with claim 32 wherein the target hydrocarbon compoundcomprises a chlorinated propene.
 36. The method in accordance with claim32 wherein the tertiary halogenated hydrocarbon impurity comprises atertiary halogenated alkane or alkene having a beta hydrogen.
 37. Themethod in accordance with claim 32 wherein the tertiary halogenatedhydrocarbon impurity comprises a member selected from the groupconsisting of 2-chloro-2-methylepentane, 2-chloro-2,3-dimethylbutane and4-chloro-4-methyl-1-pentene.
 38. The method in accordance with claim 32wherein said contacting comprises feeding the first mixture containingthe tertiary halogenated hydrocarbon impurity into a reactor defining areaction zone containing the catalyst.
 39. The method in accordance withclaim 38, further comprising passing a stripping gas stream through thereaction zone.
 40. The method in accordance with claim 39: wherein saidfeeding comprises feeding a flow stream comprising a liquid mixtureincluding the tertiary halogenated hydrocarbon impurity through thereaction zone at a rate of from 0 to about 4000 weight hourly spacevelocity (WHSV) or feeding a flow stream comprising a gaseous mixtureincluding the tertiary halogenated hydrocarbon impurity through thereaction zone at a rate of from 0 to about 4000 hr-1 gas hourly spacevelocity (GHSV); wherein said contacting comprises contacting themixture containing the tertiary halogenated hydrocarbon impurity withthe dehydrohalogenation catalyst at a temperature of from about 20 toabout 200° C. and at a pressure of from about 0.5 to about 50 psia; andwherein said passing comprises passing the stripping gas stream throughthe reaction zone at a rate of from 0 to about 4000 hr-1 gas hourlyspace velocity (GHSV).
 41. The method in accordance with claim 32wherein the dehydrohalogenation catalyst comprises a sorbent-typedehydrohalogenation catalyst selected from the group consisting ofactivated alumina, sintered alumina, activated clay, fumed silica,silica gel, magnesium silicate, TiO₂, Al₂O₃, ZrO₂, AlPO₄ andAl_(x)Si_(y)O_(z).
 42. The method in accordance with claim 41 whereinthe dehydrohalogenation catalyst is doped with a metal.
 43. The methodin accordance with claim 32 wherein the conversion is conducted at atemperature of from about 20 to about 150° C.
 44. The method inaccordance with claim 32 wherein the conversion is conducted at apressure of from about 0.5 to about 50 psia.
 45. A process comprisingsubmitting data to a governmental authority in order to obtain productregistration approval for a product comprising a member selected fromthe group consisting of the purified cis-1,3-dichloro-1-propene fractionof claim 1, the purified trans-1,3-dichloro-1-propene fraction of claim1, the purified 1,3-dichloro-1-propene mixture of claim 2, the purifiedcis-1,3-dichloro-1-propene fraction of claim 15, the purifiedtrans-1,3-dichloro-1-propene fraction of claim 15, the purifiedcis-1,3-dichloro-1-propene fraction of claim 31, the purifiedtrans-1,3-dichloro-1-propene fraction of claim 31 and the purifiedtarget hydrocarbon of claim 32.